Geochemical and stable isotope patterns of calcite cementation in the Upper Cretaceous Chalk, UK: Direct evidence from calcite-filled vugs in brachiopods

The history of research into the cementation of the Upper Cretaceous Chalk of the UK is reviewed. Calcite-filled vugs within the shell cavities of terebratulid brachiopods from the Cenomanian Chalk of eastern england have been investigated by cathodoluminesence imaging, staining, electron microprobe and stable isotope analysis. This has provided the first detailed analysis of the geochemistry of the Chalk.s cement. two cement series, suboxic and anoxic, are recognized. Both start with a Mg-rich calcite with positive [delta^13]C values considered to have been precipitated under oxic conditions influenced by aerobic ammonification. The suboxic series is characterized by positive [delta^13]C values that became increasingly so as cementation progressed, reaching values of 3.5[per mil]. Manganese is the dominant trace element in the earlier cement, iron in the later cement. Mn-and Fe-reducing microbes influenced cement precipitation and the trace element and [delta^13]C patterns. The anoxic series is characterized by [delta^13]C values that became increasingly negative as cementation progressed, reaching values of .6.5[per mil]. Trace elements are dominated by iron and manganese. Sulphate-reducing microbes influenced cement precipitation and the trace element and [delta^13]C patterns. Both cement series are related closely to lithofacies and early lithification pre-dating the regional hardening of the Chalk. The suboxic series occurs in chalk which was continuously deposited and contained hematite pigment and limited organic matter. The anoxic series was associated with slow to nil deposition and hardground development inc halks that originally contained hematite pigment but no longer do so, and an enhanced supply of organic matter